Polychloro derivatives of monocarboxy pyridines

ABSTRACT

NOVEL POLYCHLORODERIVATIVES OF MONOCARBOXY AND DICARBOXY PYRIDINES AND THEIR AMINO DERIVATIVES, THEIR METHODS OF PREPARATION AND UTILIZATION AS PESTICIDES AND INTERMEDIATES ARE DISCLOSED.

United States Patent 3,637,716 POLYCHLORO DERIVATIVES OF MONOCARBOXYPYRIDINES Russell M. Bimber, Painesville, and Paul H. Schuldt,

Mentor, Ohio, assiguors to Diamond Shamrock Corporation, Cleveland, OhioNo Drawing. Filed July 9, 1969, Ser. No. 840,484

Int. Cl. C0741 31/36 US. Cl. 260-295 R 5 Claims ABSTRACT OF THEDISCLOSURE Novel polychloroderivatives of monocarboxy and dicarboxypyridines and their amino derivatives, their methods of preparation andutilization as pesticides and intermediates are disclosed.

FIELD OF THE INVENTION This invention relates to new compositions ofmatter and methods for their preparation, and more particularly to aclass of novel chemical compounds useful as pesticides and as chemicalintermediates.

SUMMARY OF THE INVENTION This invention presents novel compositions ofsubstituted pyridines of the general formula where X is halogen, n is aninteger of one to three and R is selected from among like or unlikeradicals of the carboxylate group including acids, acid chlorides, saltsand esters thereof, or an amino radical with the provision that n isgreater than one when an R is in the 4-position, and with the provisionthat when an amino group is in the 4-position and n is two, acarboxylate group is not in the 2-position. The invention also includesnovel methods of preparing these compositions and their utilization aschemical intermediates and as pesticides.

From the foregoing discussion, it is a principal object of thisinvention to provide a new, more economical intermediate for thesynthesis of amino-substituted chlorinated picolinic acids.

An additional object of this invention is to provide novel compoundsuseful as flame retardant additives in paint and plastic formulationsand as chemical intermediates for new and improved pesticides,herbicides, plant growth regulants, flame retardant (ester) solvents,dye assistants, polyester and polyamide plastics, etc.

Other objects and properties of these substituted pyridines will becomeapparent from the following discussion, the included examples and theappended claims.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel compounds of thisinvention are substituted pyridines of the formula where X is halogen, nis an integer of one to three and R is selected from among like orunlike radicals of the carboxylate group including acids, acidchlorides, salts and esters thereof or an amino radical, with theprovision that n is greater than one when an R is in the 4-position,

3,637,716 Patented Jan. 25, 1972 ice 01 I OOOH Tetrachloropicolinic acidTrichlorolutidinic acid 0 O OH Methyl tetrachloropicolinate Monoammoniumtrichlorodipicolinate Dimethyl trichlorodipicolinate or 01 f i 0 moo-t NiL-oon,

Tetrachloronicotinyl chloride 0 01 i JCl o1 J -OI N Methyltetrachloronicotinate I 0 G1 I ilOCH;

Potassium tetrachloropicolinate Monopotassium trichlorodipicolinate HOOCC1 CIQ Dipotassium trichlorodipicolinate Dipotassium trichlorolutidinatedihydrate Trichlorodinicotinyl dichloride Dipotassiumtrichlorodinicotinate Z-Aminotrichloroisonicotinic acid4-Amiuitrichloronicotinic acid Potassium 4-aminotrichloronicotinate 0 I-V-iiO K 4-Aminodichlorodipicolinic acid Monopotassium4-aminodichlorodipicolinate c1- 01 l? 'l| 1100 N 00 1( Dipotassium4-aminodichlorodipicolinate Potassium 2-aminotrichloroisonicotinate o iio x Trichlorodipicolinic acid H000 ooo11 N Trichlorodinicotinic acidHOOC- -COOH As used in the specification and claims, the terms pesticideand pesticidal are intended to refer to the killing and/or control oforganisms and plants, such as insects, Weeds, nematodes, microorganisms,fungi or the like. Thus it will be appreciated that applications ofthese compounds are commonly termed herbicidal, insecticidal,fungicidal, nematocidal or the like.

While it is possible to apply the compounds in undiluted form to thelocus to be protected or the pest to be eradicated, it is frequentlydesirable to apply them in admixture with either solid or liquid inertadjuvants. Thus, they can be applied to the plants for fungicidalpurposes, for example, by spraying the plants with aqueous or organicsolvent dispersions of the compound. Similarly, Wood surfaces can beprotected by applying a protective film of the compound by brushing,spraying or clipping, utilizing a liquid dispersion of the compound. Thechoice of an appropriate solvent is determined largely by theconcentration of active ingredient which it is desired to employ, by thevolatility required in a solvent, the cost of the solvent and the natureof the material being treated. Among the many suitable organic solventswhich can be employed as carriers for the present pesticides, there maybe mentioned hydrocarbons such as benzene, toluene, xylene, kerosene,diesel oil, fuel oil, and petroleum naphtha; ketones such as acetone,methyl ethyl ketone and cyclohexanone; chlorinated hydrocarbons such ascarbon tetrachloride, chloroform, trichloroethylene andperchloroethylene; esters such as ethyl acetate, amyl acetate and butylacetate; the monoalkyl ethers of ethylene and diethylene glycol, e.g.,the monomethyl or monoethyl esters; alcohols such as ethanol,isopropanol and amyl alcohol; and the like.

The pesticidal compounds can also be applied to plants and othermaterials along with inert solid adjuvants or carriers such as talc,pyrrophyllite, attapulgite, kieselguhr, chalk, diatomaceous earth, lime,calcium carbonate, bentonite, kaolinite, cottonseed hulls, wheat flour,soybean flour, pumice, tripoli, wood flour, walnut shell flour andlignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of this invention. Such surface active agentsare advantageously employed in both the solid and liquid compositions.The surface active agent can be anionic, cationic or nonionic incharacter.

Typical classes of surface active agents include alkyl sulfonates,alkylaryl sulfonates, alkyl sulfates, alkylamide sulfonates, alkylarylpolyether alcohols, fatty acid esters of polyhydric alcohols, ethyleneoxide addition products of such esters, addition products of long chainmercaptans and ethylene oxide, sodium alkyl benzene sulfonates hav- 14to 18 carbon atoms, alkylphenolethylene oxides, e.g., pisooctylphenolcondensed with 10 ethylene oxide units; and soaps, e.g., sodium stearateand sodium oleate.

The solid and liquid formulations can be prepared by any suitablemethod. Thus, the active ingredients, in finely divided form if a solid,may be tumbled together with finely divided solid carrier.Alternatively, the active ingredient in liquid form, includingsolutions, dispersions, emulsions, and suspensions thereof, may beadmixed with the finely divided solid carrier in amounts small enough topreserve the free-flowing property of the final dust composition.

When solid compositions are employed, in order to obtain a high degreeof coverage with a minimum dosage of the formulation, it is desirablethat the formulation be in finely divided form. The dust containingactive ingredient usually should be sufficiently fine that substantiallyall will pass through a ZO-mesh Tyler sieve. A dust which passes througha 200-mesh Tyler sieve also is satisfactory.

For dusting purposes, preferably formulations are employed in which theactive ingredient is present in an amount of to 50% of the total byweight. However, concentrations outside this range are operative andcompositions containing from 0.1 to 99% of active ingredient by weightare contemplated, the remainder being carrier and/or any other additiveor adjuvant which may be desired. It is often advantageous to add smallpercentages of surface active agents, e.g., 0.1 to 1% of the totalcomposition by weight, to dust formulations.

For spray applications, the active ingredient may be dissolved ordispersed in a liquid carrier, such as water or other suitable liquid.The active ingredient can be in the form of a solution, suspension,dispersion or emulsion in aqueous or nonaqueous medium. Desirably, 0.5to 1.0% by weight of a surface active agent is included in the liquidcomposition.

For adjuvant purposes, any desired quantity of surface active agent maybe employed, such as up to 250% of the active ingredient by weight. Ifthe surface active agent is used only to impart wetting qualities. Forexample, to the spray solution, as little as 0.05% by weight or less ofthe spray solution need be employed. The use of larger amounts ofsurface active agent is not based upon wett ng properties but is afunction of the physiological behavior of the surface active agent.These considerations are particularly applicable in the case of thetreatment of plants.

In liquid formulations the active ingredient often constitutes not over30% by weight of the total and can be 10%, or even as low as 0.01%.

The pesticidal compounds of the present invention can be employed incompositions containing other pesticides, more especially fungicides,insecticides, and bactericides, e.g., tetrachloroisophthalonitrile,pyrethrum, rotenone, DDT, etc.

Some of the foregoing novel compounds are prepared in general byhydrolysis of the corresponding nitriles, the perchlorinatedmonomethylpyridines or perchlorinated dimethylpyridines. The hydrolysiscan be with or without the advantage of a catalytic acid with thepreferred catalytic aid being an acidified aqueous solution with anespecially preferred catalytic aid being a warm sulfuric acid solution.The hydrolysis step can also be assisted by employing heat and/orapplication of pressure between 20 to 200 C. and 0 to 200 pounds persquare inch gauge. Atmospheric or autogeneous pressure is normallyemployed, but pressurizing (e.g., with carbon dioxide) to suppressdecarboxylation is beneficial in some cases. The resulting precipitatesof colorless solids are the novel chlorinated pyridines of thisinvention.

Another method of preparing the carboxypolychloropyridine compounds isby heating the corresponding monoor dicyanopolychloropyridine in aqueous80% sulfuric acid until dissolved and then diluting the solution withice water to derive the colorless solid precipitate o f thecorresponding carboxypolychloropyridine. The appropriatecyanopolychloropyridines are known along with their preparation as setforth in US. Pat. 3,325,503, the disclosure of Which is incorporatedherein by reference.

The common mineral acids suflice to produce the acidification desiredfor the hydrolysis preparation of the polychloropicolinic acids. Typicalacids producing the desired acidification include the mineral acids suchas hydrochloric acid, sulfuric acid, and phosphoric acid. While anyproportions of the corresponding cyanopolychloropyridine and water (withacidic catalytic aid) can be reacted, it is preferred that an excess ofwater be employed in the reaction because this insures completion of thereaction. It is envisioned that the instant invention can be conductedin a batch-type process when the initial reactants are added to thereaction chamber and are reacted under the desired conditions until thereaction stops with subsequent separation of the reaction products.However, the best advantages of the instant invention will be achievedin a reactor designed to have continuous reaction by coordinatedaddition of controlled amounts of the reactants (the appropriatecyanopolychloropyridines and an aqueous mineral acid) with coordinatedwithdrawal of the reaction products.

It has also been discovered that the novel, chlorinated monocarboxy anddicarboxy pyridines of the instant invention are especially usefulintermediates in the preparation of aminopolychloropyridine carboxylicacids. In general, the preparation of the appropriateaminopolychloropyridine carboxylic acids is achieved by subjecting thecorresponding polychloropyridine carboxylic acid to an amination stepwith use of heat and/or pressure, followed by acidification which yieldsa colorless precipitate. For convenience of reaction, an ammoniasolution in water is usually employed at an appropriatte temperaturerange, e.g., 20 to 200 C., and a pressure range of 0 to 200 pounds persquare inch gauge. When the reactions are conducted at elevatedtemperatures in closed systems, the autogeneous pressure is adequate andno applied pressure is required.

Aminopolychloropyridine carboxylic acids and derivatives thereof mayalso be prepared by reacting polychlorocyanopyridines with aqueousammonia to effect both hydrolysis of the nitrile group and replacementof chlorine in a single operation. The reaction mixture may beevaporated to yield the ammonium salt, acidified with a mineral acid toobtain the desired acid, or treated in conventional ways to obtain othersalts, esters, etc.

When salts of the polychloropyridine carboxylic acids 8 EXAMPLES 2-5Preparation of polychloropyridine monoand dicarboxylic acids fromcorresponding polychlorocyanopyrior aminopolychloropyridine carboxylicacids are desired, 5 din the foregoing process may be modified so thatthe acid hydrolysis step is replaced with an alkaline hydrolysis Usmgthe eqlllpment and P P descflbed 1n step, using the hydroxide of thedesired cation to make ample 1, i P y q y lqy i y lthe salt ofpolychloropyridine carboxylic acid or aminochloropyfldlnei l yflotrlchloropyr dme, 2,6 dlpolychloropyridine carboxylic acid. Forconvenience, an 10 cyanotrlchloropyndme and d1cyapotrlchloropyrldmeiaqueous solution of the base is usually employed. The were added to toParts y Welght of an aqueouls appropriate bases and their correspondingcations 80% sulfuric acid solution and heated near 100 C. until ployedare potassium hydroxide (potassium), sodium d1$$0 1Ved t0 Product isPrecipltated y hydroxide (sodium), lithium hydroxide (lithium),ampouring the solution into ice water. It is filtered, rinsed moniumhydroxide (ammonium), etc. Careful control 15 and dried as practiced inExample 1. The products were of the reaction conditions is required insome cases to identified by infrared spectroscopic analysis and chlorineavoid replacing some of the chlorine atoms by amino 0r determinations.Table 1 sets forth the result of these prephydroxyl groups. arations.

TABLE 1 Percent chlorine content Melting point Example Reactants Productof product, C. Found Calculated 2 3-cyanotctraehloropyrldine andTctraehlorouieotinic 174.5-176 64.2 54.4

80% aqueous sulfuric acid. acid. 3 2,4-dicyan0trichloropyridineTrichlorolutidinie aeid 208-210 39.5 39.3

an r(1180% aqueous sulfuric 3-01 4 2,G-dieyanotriehloropyridineTrichlorodipicolinic 167-168 39.7 39.3

and 80% aqueous Sulfuric acid. 9.01 5 3,S-dicyanotrichloropyrldineTriehlorodinicotinie 265-266 38.4 39.3

and 80% aqueous sulfuric ac acid.

The preparation of the aminopolychloropyridine di- EXAMPLE 6 carboxylicacids or appropriate salts of aminopolychloropyridine dicarboxylic acidsfrom the polychloropyridine dicarboxylic acids of this invention isenvisioned as possible to be conducted in batch-type processes whereinthe initial reactants are added to the reaction chamber and reactedunder the desired conditions until the reaction stops, with thesubsequent separation of the reaction products. However, the bestadvantages of the instant invention will be achieved in a reactordesigned to have continuous reaction by coordinated addition ofcontrolled amounts of reactants with coordinated withdrawal of thereacton products.

In order that those skilled in the art may more completely understandthe present invention and the preferred methods by which the same may becarried into eifect, the following examples are offered in whichidentification of all compounds was done by infrared spectros copy andpartial elemental analysis.

EXAMPLE 1 Preparation of tetrachloropicolinic acid fromZ-cyanotetrachloropyridine About 0.5 gram of 2 cyanotetrachloropyridineis added to 50 ml. of warm 80% aqueous sulfuric acid in a Pyrex flaskand heated on a steam bath for 3 hours and 45 minutes, giving a clearcolorless solution. Stirring this into excess ice precipitated acolorless solid which was filtered 01f, rinsed with distilled water andair dried overnight. The resulting product melted at 179 to 180 C. withevolution of gas. This solid was identified as2-carboxytetrachloropyridine (or tetrachloropicolinic acid) as shown byconversion to 4 aminotrichloropicolinic acid and comparison of aninfrared spectrum of this product with an infrared spectrum of a knownsample of 4 aminotrichloropicolinic acid. Analytical data gave 54.2%chlorine and 5.7% nitrogen compared to a calculated 54.4% chlorine and5.4% nitrogen.

Preparation of methyl tetrachloropicolinate EXAMPLE 7 Preparation ofdimethyl trichlorodipicolinate The procedure in Example 6 was followedwith substitution of ammonium trichlorodipicolinate for the ammoniumtetrachloropicolinate used in Example 6 and recrystallization fromhexane instead of washing with distilled water to give a 67.1% yield ofpure dimethyl trichlorodipicolinate. Analysis gave 36.3% carbon and 2.2%hydrogen compared with a calculated theoretical 36.2% carbon and 2.0%hydrogen, melting at 75-76 C.

EXAMPLE 8 Preparation of monoammonium trichlorodipicolinate A solutionof 0.027 mole of trichlorodipicolinic acid and 150 ml. of aqueousammonia was heated at 90100 C. in a pressure bottle on a steam bath fortwo hours. The product was dissolved in a dilute ammonium hydroxidesolution, precipitated with concentrated hydrochloric acid and washedwith water, yielding pure monoammonium trichlorodipicolinate, melting at226-228 C. Analytical data gave 29.0% carbon, 1.9% hydrogen and 37.8%chlorine with calculated theoretical carbon being 29.2%, hydrogen 1.8%and chlorine 37.0%.

9 EXAMPLE 9 Preparation of Z-aminotrichloroisonicotinic acid Using theprocedure of Example 8, 0.027 mole of tetrachloroisonicotinic acid wassubstituted for the triyield of 60.6% pure trichlorodinicotinylchloride, melting at 61-625 C. Analytical data gave 57.2% chlorinecompared with a calculated theoretical 57.7% chlorine.

EXAMPLE 14 5 chlorodipicolinic acid of Example 8 with heating in anPreparation of methyl tetrachloronicotinate o i u n u l autoclavc j g Fandihprissure of g l A solution of 0.05 mole of tetrachloronicotinylchloride perhsfluare P; t q i h 621.1011 in methanol was added dropwiseto a solution containl g fi i a1 33 9 ing 0.05 mole of sodium methylateand methanol. The g i3 2?% fi g 3 (pig' ig jl reaction was heated atabout 65 C. for two hours. The

e 3 a 2 2 e 1 1 and nitrogen, 11.6. Found (percent): Chlorine, 44.1 andreactlon mlxture was pPured mto Water and the product was recrystalhzedfrom hexane, yielding 36% nitrogen, 11.5. pure methyltetrachloronicotinate meltin at 7273.5 C.

EXAMPLE 10 g Analytical data is: Calculated for C H Cl NO: 30.6%

Preparation of 4-aminotrichloronicotinic acid i g1;%gi hydrogen Found'304% carbon and 0 0 Otherwise following the procedure of Example 8,0.027 XAM L S 25 mole of tetrachloronicotinic acid was substituted forthe Addt. 1 d d b trichlorodipicolini-c acid of Example 8 with heatingin an (Hf ltlona fi grepare y reaclmgha autoclave at around 120 c. for18 hours at 130-149 g f i f 6 1 1 f p.s.i. pressure with the samepurification technique, yieldota E i or 6 S ing 51.7% pure4-aminotrichloronicotinic acid, melting at g 2 g 9 2 e k 2 0 .i a188-190 0. Analytical data gave 44.0% chlorine and heatgd to dgissollleg fi F i i was 11.6% nitrogen with the theoretical calculated at 44.1%filtered 0E The waters was p zg 2 23; i. zz z h or'n an .6 'tr e or iscom 11 c 1 l e d 11 m 0g n f th pou d and the res1due was oven driedunder vacuum. .Table 2 EXAMPLE 1] sets forth these preparations with thefirst column being the example numbers, the second column listing thepre- Preparat10n of 4'ammodlchlorodlp 1Chmc acld cursors, the thirdcolumn listing the product, the fourth Using the procedure of Example 8,but heating for 17 column being the melting point of the product, andthe hours rather than 2 hours, 0.027 mole of trichlorodififth columnpresenting the analytical data for each picolinic acid was converted, at110 p.s.i. pressure, to compound.

TABLE 2 Melting gong: Percent chlorine O 1' C m Example ReactantsProduct p 0 PC Found Calculated 15 Ttigi gchloropieolinlc acid and 1equivalent of Postassium tetrachloropicolinate 360 46.6 47.4 16 Trgielalrodipicolmic acid and 1 equivalent of Monopo assiumtrichlorodipicolinate; 360 35.4 34,5 17 Tergciiloronicotmie acid and 1equivalent of Potassium tetrachloronicotinate 325-329 46,5 47 4 13Trlizcglfiiodi ieolmie acid and 2 equivalents of Dipotassiumtrichlorodipicolinate 360 30.0 30.7 19 Tigigeglfir nlutidinie acid and 2equivalents of Dipotassium trichlorolutidinate dihydrate -300 27.5 27,820 'rr cgi inninicnunia acid and 2 equivalent ofDipotassiumtrichlorodinicotinate 29.9 30.7 214-aiinixngtfrlichloronicotinic acid and 1 equivalent Potassi m4-aminotrichloronicotinate 360 36.8 as. 0 22 Tii agi mdininntinia acidand 1 equivalent of Monopotassium trichlorodinicotinate 360 34.7 34.5 23i-n n n u uninninmni iannnia acid andlequivaleut Monopotassium4-amln0dlchlorodlpicolinate.. 360 25.0 24.5 242-amlinottritcl'ligggsonicotinic acid and 1 equi- Potassium 2aminotrihloroisonicotinate 320 38.1 38.0

0 25 4-2iYIl ll1 :JCP%lgg)dipl0O1iniC acid and 2 equiva- Dipotassium4-amluodichlorodipicolinate 360 30.3 2L7 en S O 1 1 Decomposes at 330 C.64.6% pure 4-aminodichlorodipicolinic acid, melting at EXAMPLE 26l85-186 C. Analytical data showed 27.4% chlorine and 11.3% nitrogenpresent and a theoretical calculation of 28.2% chlorine and 11.2nitrogen.

EXAMPLE 12 Preparation of tetrachloronicotinyl chloride EXAMPLE 13Preparation of trichlorodinicotinyl chloride The same procedure used inExample 12 was practiced here with substitution of trichlorodinicotinicacid for the tetrachloronicotinic acid used in Example 12, giving a Redspider mite spray plus systemic test This test determines theinsecticidal activity of the compound being tested against the redspider mite, Tetranychus sp. A test formulation containing 0.1 g. of thetest chemical (or 0.1 ml. if a liquid), 4.0 ml. acetone, 2.0 ml. stockemulsifier solution (0.5% Triton X- in water by volume), and 94.0 ml.distilled water is prepared for both the drench and spray treatments.The stock culture of mites is maintained on Scarlet runner bean foliage.Approximately 18 to 24 hours before testing, mites are transferred fromthe stock culture on pieces of infested leaves which are placed on theprimary leaves of two lima bean plants (var. Sieva) grown in 2 /2-inchpots. As leaf fragments dry, the mites migrate to the unfested leaves.Immediately before drenching and spraying, the leaf fragments areremoved from the foliage.

For spray application, 50 ml. of the test formulation is sprayed bymeans of a DeVilbiss paint spray gun (Type CH), calibrated to deliver 45ml. water in 30 seconds at 30 pounds air pressure per square inch, whilethe plants are being rotated on a turntable in a hood. After 11 threedays, two of the four leaves treated are examined under a binocularsteroscopic microscope and the mortality determined. Using thisprocedure, the following results are obtained:

Compound Trichlorodinicotinyl chloride:

Dosage, p.p.m. 500 Percent mortality mite spray 75 EXAMPLE 27 Houseflyspray test This test determines the insecticidal activity of thecompound being tested against adult housefiies, Musca domestica.

The formulation for this test contains 0.1 g. of test chemical (or 0.1ml., if a liquid); 4.0 ml. acetone, 2.0 ml. stock emulsifier solution(0.5% Triton X-l55 in water by volume) and 94.0 ml. distilled water. Theconcentration of toxicant in this formulation is 1000 p.p.m., with lowerconcentrations being obtained by diluting the formulation with distilledwater.

Cages consisting of cylindrical screens 1% inches in diameter by 4inches long are fabricated from 20-mesh stainless steel screening. Oneend is closed with a size D polyurethane foam tube plug. Ten adulthousefiies (male and female), anesthetized with carbon dioxide, arecounted into each cage, and the open end is then closed with a secondfoam plug. The cages are inserted into a wire stand mounted in theturntable in the spray hood and the insects are sprayed with 50 ml. ofthe formulation. The flies are supplied a dextrose solution by draping apaper wick over the outside of the screen cylinder. They are able tofeed and drink by passing their probosoi through the openings in thescreen. Mortality data are recorded three days after treatment. Resultsof insecticidal activity are given in the following table:

Compound tested Trichlorodinicotinyl chloride:

Concentration, p.p.m. 500

The plants used for this test are planted in 3 /2 inch pots as follows:

(a) Tomato, var. Bonny Best, one plant per pot;

(b) Garden bean, var. Tendergreen, four plants per pot; (c) Field corn,var. Cornell M-3, four plants per pot; (d) Oats, var. Russell, 15 toplants per pot.

The various test species are planted so that at treatment time they areat the following stages of growth:

(a) Tomato-three to five inches tall;

(b) Beanthe first trifoliate leaf begins to unfold; (c) Corn-four to sixinches tall;

(d) Oats-three to five inches tall.

In the soil drench treatment the soil surface of each pot (tomato, bean,corn, and oats) is drenched with 17.5 ml. of the test compound,resulting in an application of 64 pounds per acre with dilution to givethe lower concentrations tested. The four pots are then sprayedsimultaneously with the remaining ml. of formulation on a rotatingturntable in a hood at 40 p.s.i. This foliage spray contains 2400 p.p.m.of chemical or about two pounds of active chemical per gallons of watersolution with dilution to give the lower concentrations tested. Afterthe plant foliage dries, the plants are placed in the greenhouse. Theresults are recorded fourteen days after treatment. Phytotoxicity israted on the scale from 0, indicating no plant injury, to 11, plant killand, additionally, stunting of the plant is rated on a scale of 1slightto 9-severe. Chemicals found to give a phytotoxicity rating of 10 ormore or a stunting rating of 9 on one or more of the test species areretested at lower rates. On retesting, the soil drench and foliage spraytreatments are carried out as separate tests. Only those species onwhich suitable ratings were obtained for phytotoxicity or stunting orboth are retained for testing at lower dosages and the remaining speciesare dropped from further testing. Other responses such as formativeeffects (Fe), defoliant activity (Da), growth-regulant properties, andchlorosis (Ch) are recorded. Using this procedure, the following resultsare Percent mortality 40 obtained:

TABLE 3 Phytotoxicity and other effects Dosage Soil watering Foliagespray Compound Lbs/A. P.p.m. B0 0 2 'letrachloropicolinic acid 64 2, 400Methyl tetrachloropicoliuatc 64 2, 400 Monoamrnonium trichlorodipicolinaPotassium tetracl1l0ropicolinate Gt 2, 400 Potassiumtetrachloronicotinatc 64 2, 400 Potassium trichlorolutidinate dihydrate8 300 4 150 Potassium trichlorodinicotinato 64 2, 400 64 2, 4002-aminotrichloroisonieotinic acid 32 1, 200 16 600 Potassium4-aminotricliloronicotiuato 64 2, 400 4-amiuotrichlorouicotinic acid...64 2, 400 6-1 2, 400 4-aminodiclllorodlpicoliuic acid 32 1,200 16 600 8300 Monopotassium 4a1ninodichlorodipicolinate {64 2, 400 8 300 Potassium2-aminotrlchioroisonicotinate 2, 400 600 Dipotasslum4-aminodiehlorodipicolinate {6; 2, 400 300 Triclllorodipicolinic acid 64I 2 400 l Stunts beau plants at this concentration.

EXAMPLE 28,

Soil drench and post-emergence foliage spray combination To measure thefoliage contact and soil drench herbicidal activity of compounds of thisinvention, a test formulation of 150 ml. is prepared for both thesoildrench and foliage spray treatments. This formulation contains 0.36g. of the test chemical (or 0.36 ml. if a liquid), 6.0 ml. acetone, 3.0ml. stock emulsifier solution (0.5% Triton X- in water by volume), and141.0 ml. distilled water.

EXAMPLE 29 Viruscide test 13 host virus systems, southern bean mosaic onPhaseolus vulgaris var. Pinto and maize dwarf mosaic virus on Zea maysvar. Golden X Bantam, are cultured in the same four-inch clay pot. Virusinoculation is made by carborundrum leaf abrasion method prior totreatment.

In the foliage spray application, 33 ml. of the test formulation (1000p.p.m. with dilution to lower concentrations) are sprayed at 40 poundsper square inch air pressure While the plants are being rotated on aturntable in a hood. Twenty-four hours after spraying, in the soildrench treatment, the test formulation is applied at the soil surface ofeach pot; 45 ml. of the formulation being equivalent to a dosage of thetest chemical of 64 pounds per acre with lower concentrations for testmade by dilution. Effective control is determined through visualobservation of the presence or absence of viral infection symptoms tendays after inoculation. Using this procedure, the following results areobtained:

Percent control and other effects Post-emergence Pre-emergence bean haloblight (Pseudomonas phaseolicola). A test formulation of 150 ml. isprepared for both the soil drench and foliage spray treatments. Thisformulation Soil drench Percent control Dosage Foilage spray CompoundLbs/acre p.p.m. Corn Bean Corn Bean Potassium trichlorodinicotinate 64l, 000 100 100 Triehlorodinicotinyl chloride. 500 1002-aminotrichloroisonicotinic ac 500 100 100 Potassiumaraminotrichloronicotinate 1, 000 100 100 100 100 ontains 0.36 ram 0 hetes EXAMPLE 5 c g s f t t chemical, 60 acetone,

Preand post-emergence tests in soil, broadleaf and grass species Thistest measures the preand post-emergence herbicidal activity of testchemicals applied to the foliage of seedling plants, as well as to thesoil in which they are growing. Seeds of six species are planted in soilcontained in 9 x 9 x 2-inch aluminum cake pans filled to Within /2-inchof the top with composted greenhouse soil. The seeds planted consist ofthree broadleaf species (buckwheat, Fagopyrum esculentum, turnup,Brassica rapa, and Zinnia Zinnia spp.) and three grass species (sorghum,Sorghum vulgare, Italian millet, Panicum romosum, and perennialryegrass, Lolium perenne). The soil in each pan is divided into twoequal rectangular areas, and the broadleaves are seeded into one-half ofone of these areas and the grasses into the other half of the same area.The seeds are then covered uniformly with about one-fourth inch of soiland watered, after which they are removed to the greenhouse and the testspecies are allowed to grow until one true leaf is present on theslowest broadleaf (Zinnia). This requires between 7 and 14 daysdepending upon the time of the year. When the plants (seedlings) havereached this stage of development, and one day prior to spraying, theother halves of the pans are planted as before, but broadleaves andgrasses are reversed.

The pans are then sprayed at 10 p.s.i., uniformly covering the surfaceof the soil and the foliage with 40 3.0 ml. stock emulsifier solution(0.5% Triton X-lSS in water by volume), and 141 ml. distilled water. Theplants used for this test, garden bean var. Tendergreen, four plants perpot, are planted in 3 /2-inch pots. At treatment time, the beans havereached a stage of growth such that the first trimoliate leaf begins tounfold. Two of the bean plants per pot are inoculated by injection withthe bean halo blight using a hypodermic syringe. The organism is takenoff a slant culture medium.

In the soil drench treatment, the soil surface of each pot is drenchedwith 17.5 ml. of the test compound, resulting in an application of 64pounds per acre. The four pots are then sprayed simultaneously with theremaining ml. of formulation on a rotating turntable in a hood at 40psi. This foliage spray contains 2400 ppm. of chemical or about twopounds of active chemical per gallons of water solution. After the plantfoliage dries, the plants are placed in the greenhouse. The results arerecorded 14 days after treatment. Ratings are based on a scale of 100percent for total control of the blight. Chemicals found to give a veryhigh rating in the initial test are retested at lower rates. Onretesting, the soil drench and foliage spray treatments are carried outas separate tests with the lower test concentrations being made bydilution. Using this procedure, the following results are obtained:

Dosage, Percent Dosage, Percent Compound lbs/A. control p.p.n1. controlMethyl tetrachloroplcolinate".

Monoammonium trlchlorodipicolinate Methyl tetrachloronicotinate2-aminotrichlorolsonicotinlc acid 4-aminotriehloronicotinic acid...

a-arninodichlorodipicolinic acid 15 EXAMPLE 32 Bactericides Testformulations are examined for ability to inhibit the colonial growth ofErwinz'a amylovora (E.a.), Xan- Ihomonas phaseoli (X.p.), Staphylococcusaureus (S.a.), and Escherechia coli (E.c.) at various concentrations.The basic test formulation contains 0.125 g. of the test chemical (or0.125 ml. if a liquid), 4.0 m1. acetone, 2.0 ml. stock emulsifiersolution (0.5% Triton X-155 in water by volume) and 94.0 ml. distilledwater, the concentration of toxicant in this formulation being 1250parts per million. Lower concentrations of toxicant are obtained bydiluting the basic formulation with distilled water.

Two ml. of each formulation is dispensed into a test tube which is thenplaced into a water bath maintained at 44 C. From a stock preparation(also held at 44 C.), 8 ml, of ZO-percent nutrient agar is added to thetest tube giving a 1:5 dilution or a final concentration of 250 p.p.m.chemical in the agar. The contents of the test tube are then thoroughlymixed, while still warm, with the aid of a Vortex type mixer andimmediately poured into a sterile polystyrene Petri dish (100 x 15 mm.).After the agar in the plate is set, suspensions of each organism aresimultaneously streaked onto the surface of the agar. After the plate isinoculated, it is incubated 24 to 48 hours at 30 C., after which timeeach organism is rated visually for growth inhibition by the candidatechemical. Estimates of percent growth inhibition are relative to growthof streak colonies in control plates obtained during individual tests.Using this procedure, the following results are obtained:

EXAMPLE 33 FungicidesFoliage protectant and eradicant tests The tomatofoilage disease test measures the ability of the test compound toprotect tomato foilage against infection by the early blight fungusAlternaria solani (Ell. and Mart.) Jones and Grout and the late blightfungus Phytophthora infestans (Mont.) deBary. The method used employstomato plants, to 7 inches high which are 4 to 6 weeks old. Duplicateplants, one set for each test fungus, are sprayed with various dosagesof the test formulation at 40 lbs/sq. in. air pressure while beingrotated on a turntable in a hood. The center of the turntable is 45inches from the nozzle of the spray gun. The test formulation containingthe test compound, acetone, stock emulsifier solution and distilledwater is applied at concentrations up to 2000 p.p.m. of the testchemical. Lower concentrations of toxicant are obtained by employingless toxicant and more water, thereby maintaining the same concentrationof acetone and emulsifier.

After the spray deposit is dry, treated plants and controls (sprayedwith formulation less toxicant) are sprayed while being rotated on aturntable with a spore suspension containing approximately 20,000conidia of A. solani per ml., or 150,000 sporangia of P. infestans perml. The atomizer used delivers 20 ml. in the 30-second exposure period.The plants are held in a saturated atmosphere for 24 hours at 70 F. forearly blight and 60 F. for late blight to permit spore germination andinfection before removal to the greenhouse. After two days from thestart of the test for early blight and three days for late blight,lesion counts are made on the three uppermost fully expanded leaves. Thedata are converted to percent disease control based on the number oflesions obtained on the 16 control plants. Dosages and percent diseasecontrol are given in the following table:

Compound Dimethyl trichlorodipicolinate:

Dosage percent concentration 1000 Percent disease control:

E. blight L. blight 100 EXAMPLE 34 Systemic bactericidal test Testformulations are examined for ability to control tomato crown gall(Agrobacterium tumefaciens). A test formulation containing 0.24 g. ofthe test chemical (or 0.24 ml. if a liquid), 4.0 ml. acetone, 2.0 ml.stock emulsifier solution (0.5% Triton X- in water by volume), and 94.0ml. distilled water is prepared for both the soil drench and foliagespray treatments. Individual tomato plants, var. Rutgers, are planted in3 /2-inch clay pots and are 3 to 5 inches tall at treatment time. Stempuncture inoculation, at the cotylodonary node, with a cellularsuspension of the A grobacterium tumefaciens is made one to two hoursprior to the soil drench and foliage spray treatment.

In the soil drench treatment, the test formulation is applied at thesoil surface of each pot; 17.5 ml. of the formulation being equivalentto a dosage of the test chemical of 64 pounds per acre with lowerconcentrations being achieved through dilution. Control is determinedthrough visual observation of tumor formation 10 to 14 days aftertreatment. Using this procedure, the following results are obtained:

been described with specific reference to particular embodimentsthereof, it is not to be so limited since changes and alterationstherein may be made which are within the full intended scope of thisinvention as defined in the appended claims.

What is claimed is:

1. A compound selected from the group consisting of 2amino-trichloro-isonicotinic acid, 4 amino-trichloronicotinic acid,alkali metal salts thereof and the corresponding lower alkyl estersthereof.

2. The compound according to claim 1 wherein the compound is2-aminotrichloroisonicotinic acid.

3. The compound according to claim 1 wherein the compound is potassium2-aminotrichloroisonicotinate.

4. The compound according to claim 1 wherein the compound is4-amino-trichloro-nicotinic acid.

5. The compound according to claim 1 wherein the compound is potassium4-amino-trichloro-nicotinate.

References Cited UNITED STATES PATENTS 3,285,925 11/1966 Johnston et al.260295 3,288,796 11/1966 Harrison 260295 3,325,272 6/1967 Hamaker et a1.712.5

OTHER REFERENCES Chambers et al., J. Chem. Soc., London, pp. 50405,September 1965.

ALAN L. ROTMAN, Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,637,716 Dated January 25, 1972 Inventor(s) Russell M. Bimber and PaulH. Schuldt It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 3, lines 40-45, that formula reading C1 C1 9 2 9 9 c1c -cc1 010C01 should read cl-- -c1 c1 c1 Column 5, line 69, change For" to for-Column 6, line 65, change "appropriatte" to -'-appropriate-; Column 7,line &8, change "reacton" to --reaction--; Columns 9 and 10, Table 2,Example 20, under heading "Reactants" change "equivalent" to--equivalents-; Columns 9 and 10, Table 2, Example 25, under heading"Percent Chlorine" subheading "Found" change "30.8" to --20.8--; Column10, lines 57-58, "Tetranychus sp." should be italicized; Column 10, line68, chan e 'unf'ested to --uninfested; Column 11, line 50, chan e "in"%first occurrence) to --on--; Column 11, line 34, change probosoi" to--probosci-; Column 11, line 66, delete after "EXAMPLE 28"; Columns 11and 12, Table 3, under subheading "Foliage Spray" change "a0" to -Oa--;Columns 11 and 12, Table 3, under subheading "Foliage Spray" secondsubheading "Be enter -O-- for compound potassium trichlorolutidinatedihydrate; Columns 11 and 12, Table 5, last column change "4 to 4 Column13, lines 5 and 6, change "carborundrum" to --carborundum--; Column 1 4,line 41, change "trimoliate" to --trifoliate--; Column 14, lines 65-70,should read:

(continued) F ORM PO-105O (10-69) USCOMM-DC 60376-P69 a u.s. GOVERNMENTPRINTING OFFICE: (969 0-366-334 UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent 3.637.716 Dated 1mm 25. 1972 Inventor(s) Russell M.Bimber and Paul H. Schuldt It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

--Monoa.mmonium trichloro- 2 100 37.5 100 dipicolinate 1 100 18.1 100Methyl tetrachloronicotinate 64 100 2400 100 E-aminotrichloroiso- 32 1001200 100 nicotinic acid 16 100 600 100 Signed and sealed this 5th day ofSeptember 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents F ORM PO-1050 (10-69] USCOMM-DC 60376-P69 U.S. GOVERNMENTPRINTING OFFICE: I969 0-356-334

